Arsenic and phosphorus containing polydentates

ABSTRACT

POLYDENTATE COMPOUNDS INCLUDING (1) POLYTERIARY PHOSPHINES, (2) POLYTERTIARY ARSINES, AND (3) POLYTERIARY ARSINO-PHOSPHINESD, CONTAINING FOUR OR MORE TRIVALENT PHOSPHORUS ATOMS, FOUR OR MORE TRIVALENT ARSENIC ASTOMS, AND A COMBINATION OF FOUR OR MORE TRIVALENT PHOSPHORUS ATOMS AND TRIVALENT ARSENIC ATOMS, RESPECTIVELY, WITH A BRIDGE OF TWO CARBON ATOMS, FOR EXAMPLE, -CH=CH- OR -CH2-CH2-, BETWEEN AT LEAST TWO OF THE PHOSPHORUS ATOMS, TWO OF THE ARSENIC ATOMS, AND THE PHOSPHORUS AND ARSENIC ATOM, RESPECTIVELY, AND (4) POLYTERIARY ARSINOPHOSPHINES CONTAINING AT LEAST ONE TRIVALENT PHOSPHORUS ATOM AND AT LEAST ONE TRIVALENT ARSENIC ATOM WITH A BRIDGE OF TWO CARBON ATOMS, FOR EXAMPLE, -CH=CH- OR -CH2-CH2-, BEWTEEN THE PHOSPHORUS AND ARSENIC ATOMS, SAID COMPOUNDS BEING USEFUL AS ADDITITVES IN GASOLINES AND FOR FORMING COMPLEXES WITH METAL CARBONYLS AND METAL HALIDES FOR USE AS CATALYSTS IN THE POLYMERIZATION OR OLIGOMERIZATION OF OLEFINS AND ACTEYLENES AND IN HYDROGENATION PROCESSES; AND THE BASE-CATALYZED ADDITION PROCESS OF SNTHESIZING THE FOREGOING COMPOUNDS WHEREIN THE ADDITION OF COMPOUNDS WITH PHOSPHORUS-HYDROGEN BONDS OR ARSENIC-HYDROGEN BONDS TO VINYL OR ETHYLNYL PHOSPHORUS OR ARSENIC DERIVATIVES IS BROUGHT ABOUT, EACH OF THE PHOSPHORUS AND ARSENIC BEING IN ITS TRIVALENT STATE.

United States Patent 3,657,298 ARSENIC AND PHOSPHORUS CONTAININGPOLYDENTATES Robert Bruce King, Athens, Ga., and Pramesh N. Kapoor,Pittsburgh, Pa., assignors of fractional part interest to PressureChemical Co., Pittsburgh, Pa. No Drawing. Filed Jan. 6, 1970, Ser. No.1,058 Int. Cl. C07f 9/50, 9/ 74 US. Cl. 260-440 16 Claims ABSTRACT OFTHE DISCLOSURE Polydentate compounds including l) polytertiaryphosphines, (2) polytertiary arsines, and (3) polytertiaryarsine-phosphines, containing four or more trivalent phos phorus atoms,four or more trivalent arsenic atoms, and a combination of four or moretrivalent phosphorus atoms and trivalent arsenic atoms, respectively,with a bridge of two carbon atoms, for example, CH=CH- or CH CH betweenat least two of the phosphorus atoms, two of the arsenic atoms, and thephosphorus and arsenic atom, respectively, and (4) polytertiaryarsinophosphines containing at least one trivalent phosphorus atom andat least one trivalent arsenic atom with a bridge of two carbon atoms,for example, -CH=CH-- or CH CH bewteen the phosphorus and arsenic atoms,said compounds being useful as additives in gasolines and for formingcomplexes with metal carbonyls and metal halides for use as catalysts inthe polymerization or oligomerization of olefins and acetylenes and inhydrogenation processes; and the base-catalyzed addition process ofsynthesizing the foregoing compounds wherein the addition of compoundswith phosphorus-hydrogen bonds or arsenic-hydrogen bonds to vinyl orethylnyl phosphorus or arsenic derivatives is brought about, each of thephosphorus and arsenic being in its trivalent state.

This invention relates to novel polydentate compounds includingpolytertiary phosphines, polytertiary arsines, and polytertiaryamino-phosphines, each containing four or more trivalent phosphorusatoms, four or more trivalent arsenic atoms, and a combination of fouror more trivalent phosphorus atoms and trivalent arsenic atoms,respectively, with a bridge of two carbon atoms between at least two ofthe trivalent atoms. Also, this invention relates to such polydentatecompounds as polytertiary arsine-phosphines having at least onetrivalent phosphorus atom and at least one trivalent arsenic atom with abridge of two carbon atoms between the phosphorus and arsenic atoms. Inaddition, this invention relates to a novel basecatalyzed additionprocess for making the foregoing compounds, and the process comprisesthe base-catalyzed addition of compounds with phosphorus-hydrogen bondsor arsenic-hydrogen bonds to vinyl or ethynyl trivalent phosphorus ortrivalent arsenic derivatives. The foregoing compounds containing fouror more of the trivalent atoms, as aforesaid, and containing at leastone trivalent phosphorus atom and at least one trivalent arsenic atom,as aforesaid, are made by the aforesaid novel process. In addition, theaforesaid novel process is carried out to make known polydentates havingless than four trivalent atoms, for example, two and three, wherein saidatoms are the same, for example, arsenic or phosphorus, in much higheryields than known processes and of such a nature that they can be morereadily purified than can those made by known processes. The novelpolydentate compounds, as aforesaid, are useful in forming complexeswith metal carbonyls and metal halides for use as catalysts in thepolymerization of olefins and alkynes and in hydrogenation processes togive much higher yields and higher grade products. Also, the novelpolydentate compounds ICE are useful as gasoline additives. The novelpolydentates have improved coordinating ability especially with regardto their abilities to occupy more coordination positions in formingcomplexes, for example, with metal carbonyl complexes such as used ascatalysts in hydrogenation processes.

Heretofore, polydentate compounds such as polytertiary phosphines andpolytertiary arsines have been formed by reacting an alkali metaldiarylphosphide with a 1,2-dihaloethane, for example, an alkali metaldiphenylphosphide with 1,2-dichloroethane, to obtain a ditertiaryphosphine, for example, (C H PCH CH P(C H in relatively small yields,for example, about 40%. Also, such cornpounds as the tritertiaryphosphine CsHs CH2CH2P CeHs \ CuHg CH2CH2P CuHs were made by reactingsodium diphenyl phosphide and the difficultly accessible phenylbis(2-bromoethyl) phosphine C H P(CH CH Br) in relatively small yields,for example, 15 to 16%. Heretofore, polytertiary phosphines,polytertiary arsines, and polytertiary arsine-phosphines, having four ormore trivalent phosphorus atoms, four or more trivalent arsenic atoms,and a combination of four or more trivalent phosphorus atoms andtrivalent arsenic atoms, respectively, except a hexadentate polytertiaryarsine ligand [see Harris et al., Chem. Commun., 965 (1968) with abridge of two carbon atoms, for example, -CH=CH or CH -CH between atleast two of the trivalent atoms, and polytertiary arsino-phosphineshaving at least one trivalent phosphorus atom and at least one trivalentarsenic atom with a bridge of two carbon atoms, for example, --CH=CH orCH -CH between the phosphorus and arsenic atoms, have not been known andavailable. With our novel base-catalyzed process of this invention wehave made for the first time our novel compounds, as aforesaid, and alsoknown compounds in yields higher, for example, 65-90% or greater, thanever before attained by prior art processes, for example, 15-40%, asatoresaid. Polytertiary phosphines and polytertiary arsines having nomore than two trivalent phosphorus atoms and two trivalent arsenicatoms, respectively, with bridge of two carbon atoms between the twophosphorus atoms or the two arsenic atoms are disclosed in the Wald USPat. No. 3,130,237. Said Wald patent discloses a complex of cobalt andan organo-phosphine or an organo-arsine or a mixture of anorgano-phosphine and an organo-arsine, but said Wald patent does notdisclose a complex of cobalt and an organo arsino-phosphine.

The ditertiary phosphine 1,2 bis(diphenylphosphino) ethane (C H PCH CHP('C H is disclosed by Sasse in Methoden der Organischen Chemie,Houben-Weyl, E. Muller, Ed., George Theme Verlag, Stuttgart, 1963, pp.25-28. Hewertson et al. [J. Chem. Soc., 1490 (1962)] disclose thetritertiary phosphine An object of this invention is to provide novelpolydentate polytertiary phosphines, arsines and arsino-phosphines,having four or a combination of four of the respective trivalent atoms,except a hexadentate polytertiary arsine, with a two-carbon bridgebetween at least two of the trivalent atoms, and polytertiaryarsine-phosphines having at least one trivalent phosphorus atom and atleast one trivalent arsenic atom with a two-carbon bridge therebetween,said novel compounds having greatly improved coordinating abilityespecially with regard to the C H5- P 3 ability to occupy morecoordination positions than heretofore known polydentate polyteitiaryarsine compounds and polytertiary phosphine compounds.

Another object of this invention is to provide the novel base-catalyzedaddition process for making heretofore known polydentate polytertiaryarsine compounds and polytertiary phosphine compounds in greater yieldsand in a more easily purifiable state than by heretofore known processesand for making the novel compounds, as aforesaid, wherein the additionof compounds with trivalent prosphorus-hydrogen bonds or trivalentarsenic-hydrogen bonds to .vinyl or ethynyl trivalent phosphorus ortrivalent arsenic derivatives is brought about.

Other objects and features will be readily apparent from the followingdetailed description which is not limiting but only illustrative of thepreferred embodiments of this invention.

,This application is directed to those skilled in the art to which itpertains, or with which it is most nearly connected, and sets forth thebest mode and modes contemplated by us of carrying out our invention.The heretofore known organic chemistry, for example, that relating toalkyl groups, aromatic hydrocarbon groups, alkoxy groups, dialkylaminogroups, alkoxy substituted alkyl and aromatic hydrocarbon groups, anddialkylamino substituted alkyl and aromatic hydrocarbon groups is widelyknown, that is, the nature of said groups as to the number of carbonatoms, hydrogen atoms, oxygen atoms, nitrogen atoms, etc., and it is notconsidered necessary to repeat same herein for the reason that thoseskilled in the art are aware of same without a detailed recitation ofsuch conventional and generally widely known elements or groups ofelements.

More particularly, the polydentate compounds of this invention have thegeneral formulae (1) X(AYR R 2 B R R atn) AX R{ 11 \R4 XA\ AX 1 1 R6/YAY R6 XA AX and R R 4 R X(AYRR )3-m In the foregoing compounds, X is atrivalent phosphorus atom or a trivalent arsenic atom and A is either orCR -CR R is hydrogen, an alkyl group, an aromatic hydrogen group, analkoxy substituted alkyl group, an alkoxy substituted aromatichydrocarbon group, a dialkylamino substituted alkyl group, or adialkylamino substituted aromatic hydrocarbon group, but at least one Ris hydrogen; n is a whole number of at least 2; and m is 1 or 2. Each ofR R R R R R R R R and R is an alkyl group, an aromatic hydrocarbongroup, an alkoxy substituted alkyl group, an alkoxy substituted aromatichydrocarbon group, a dialkylamino substituted alkyl group, or adialkylamino substituted aromatic hydrocarbon group.

As to the polydentate compound (1), supra, X and Y are both thetrivalent phosphorus atom or the trivalent arsenic atom, or X is thetrivalent phosphorus atom and Y is the trivalent arsenic atom, or X isthe trivalent arsenic atom and Y is the trivalent phosphorus atom. Withrespect to the polydentate compound (2), supra, X is always the same,that is, X is either the trivalent phosphorus atom or the trivalentarsenic atom, and Y is either the trivalent phosphorus atom or thetrivalent arsenic atom. As to the polydentate compound (3), supra,

X is always the same, that is, X is either the trivalent phosphorus atomor the trivalent arsenic atom, and Y is either the trivalent phosphorusatom or the trivalent arsenic atom, but the X and Y members are neverall trivalent arsenic atoms. For example, specific embodiments of thepolydentate compound (3), supra, are those having the formulae (a)phenyl phcnyl ASCHzCHg CII2CII2AS phenyl phcnyl phenyl P CH2CH2P phenylASCH2CH2 CHzCHzAS phenyl \phellyl (b) phenyl henyl P CHzCHz CHzCH Pphenyl ASCHZOHMS phonyl phenyl phonyl P 01120 2 CHzCHzP phenyl phenyland ( D y henyl P CHzCHz CH2CH2P phenyl phellyl phenyl P CHZCHZP phenylPOI-1 0E; CHzCHzP phenyl phenyl To make compound (a), supra,diphenylvinylarsine and 1,2-diphosphinoethane are reacted in accordancewith the procedure described in Example 5, infra. To make compound (b),supra, diphenylvinylphosphine and 1,2- diarsinoethane are reacted inaccordance with the procedure described in Example 5, infra. To makecompound (0), supra, diphenylvinylphosphine and 1,2-diphosphinoethaneare reacted in accordance with the procedure described in Example 5,infra.

With respect to polydentate compound (4), supra, X is either thetrivalent phosphorus atom or the trivalent arsenic atom, and Y is eitherthe trivalent arsenic atom or the trivalent phosphorus atom, but X and Yare not the same. For example, if X is the trivalent phosphorus atom, Yis the trivalent arsenic atom, and if X is the trivalent arsenic atom, Yis the trivalent phosphorus atom.

The number of carbon atoms in the aforestated alkyl groups (R, R R R R RR R R R and R can be from one through seventy, for example, methyl,ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tertbutyl,n-pentyl or n-amyl, isopentyl or isoamyl, tert-amyl, neopentyl, heXyland isomers thereof, heptyl and isomers thereof, octyl and isomersthereof, nonyl and isomers thereof, decyl and isomers thereof, undecyland isomers thereof, dodecyl and isomers thereof, through heptacontyland isomers thereof, and preferably from one through twelve carbonatoms, for example, methyl, ethyl, propyl and its isomers, n-butyl andits isomers, n-pentyl or n-amyl and its isomers, n-hexyl and itsisomers, n-heptyl and its isomers, n-octyl and its isomers, n-nonyl andits isomers, n-decyl and its isomers, n-undecyl and its isomers andn-dodecyl and its isomers.

The number of carbon atoms in the aforestated aromatic hydrocarbongroups (R, R R R R R R R R R and R can be up to twenty-four (24), forexample, phenyl, phenoxy, a-naphthyl, B-naphthyl, dinaphthyl (fromperylene or uaa'a'-dinaphthylene or fififiH-dinaphthylene), a-anthracylor fl-anthracyl or 'y-anthracyl, a-phenanthryl or B-phenanthryl or'y-phenanthryl or a-phenanthryl or e-phenanthryl, benzo[def]phenanthryl(from pyrene), and such alkyl substituted aromatic hydrocarbon groupsincluding the aforementioned alkyl groups as substituent groups, forexample, benzyl and p-tolyl, etc., and preferably phenyl, benzyl andp-tolyl.

With respect to the alkoxy substituted alkyl groups and the aromatichydrocarbon groups for R", R R R R R R R R R and R supra, the number ofcarbon atoms in the alkoxy substituent can be from one through seventy,as set forth in the alkyl groups, supra, for example, methoxy, ethoxy,etc., and preferably methoxy and ethoxy. As to the dialkylaminosubstituted alkyl groups and aromatic hydrocarbon groups for R, R etc.,the number of carbon atoms in the alkyl of the dialkylamino substituentcan be from one through seventy, as for the alkyl groups, supra, forexample, dirnethyl, diethyl, etc., for example, dimethylamino,diethylamino, etc.

The novel process. for preparing the novel polydentate compounds of thisinvention and other polydentate polytertiary phosphine and arsinecompounds involves reacting (1) a phosphine or an arsine having at leastone trivalent phosphorus-hydrogen bond or one trivalent arsenichydrogenbond, respectively, with (2) a phosphine having at least onevinyl-trivalent phosphorus bond or an arsine having at least onevinyl-trivalent arsenic bond or a phosphine having at least oneethynyl-trivalent phosphorus bond or an arsine having at least oneethynyltrivalent arsenic bond in contact with a base catalyst. However,each of the reactant compounds contemplated under (1), supra, is free ofa vinyl-trivalent phosphorus bond and a vinyl-trivalent arsenic bond andan ethynyltrivalent phosphorus bond and an ethylnyl-trivalent arsenicbond and each of the reactant compounds under (2), supra, is free of atrivalent phosphorus-hydrogen bond and a trivalent arsenic-hydrogenbond. Also, each of the reactant compounds contemplated under (1),supra, has only one trivalent phosphorus-hydrogen bond or trivalentarsenic-hydrogen bond if the reactant compound under (2), supra, has aplurality, that is, more than one, of vinyl-trivalent phosphorus bonds,vinyl-trivalent arsenic bonds, ethylnyl-trivalent phosphorus bonds orethynyltrivalent arsenic bonds. In addition, each of the reactantcompounds under (2), supra, has only one vinyl-trivalent phosphorusbond, one vinyl-trivalent arsenic bond, one ethynyl-trivalent phosphorusbond or one ethynyl-trivalent arsenic bond if the reactant compoundunder (1), supra, has a plurality, that is, more than one, of trivalentphosphorus-hydrogen bonds or trivalent arsenic-hydrogen bonds.

For example, in accordance with our novel process, in making knownpolytertiary phosphines and known polytertiary arsines having theformula Where X and Y are both phosphorus or both arsenic, the reactantcompounds are, for example,

and R R R and R can be the same or different within the scopehereinbefore described. Likewise, in another embodiment, instead of thevinyl-phosphorus or the vinyl-arsenic bond-containing compounds, theethynylphosphorus or the ethynyl-arsenic compounds.

PCECH or 14 As-CECH can be used. The reactions involving the foregoingcompounds form the product compounds, with m being the whole number 2,as follows P CH=CHP Rs io With m being the whole number one, thereactant compounds /H /R' B -P and CH2=OHP are reacted to form theproduct R9 cHioHiP Rio CH2CH2P/ \RIO and the reactant compounds R3AS andCH1=CHP H RlD are reacted to form the product e C H2 CH 2 P/ n CHZOIIQPRlfl and the reactant compounds 0 and CHECHAS Rtu are reacted to form R0CH=CHAs R9 GH=OHAs Rio Also, in still another embodiment, with m beingthe whole number one, reactant compounds are reacted with reactantcompounds to form CHz=CH CHz=CH /Rt /Rl P-RB or AsR CH2CH2P\ CH=CHP\CH1=CH CH1=CH 5 In B respectively, to form /R /R /R' P-CHzCHzP OIP-CH=CHP\ ornom-P m R7 R10 R1 R1 11 -1 or 10 01120112? CH:CHP\ CHICHr-P\R1 R2 R respectively. Also R As-CH=CH or As-CECH CHZCHZAS\ CH=CH2 CECHR10 is reacted with R5-AS 2O R R1 CHzCHzAs /As-H respectively. With inbeing the whole number one, reactant to form compounds v 9 CIIZCHQASCH=GHAS P-H or As-H 2 2 R R R10 R10 R R are reacted with reactantcompounds AS CHZCH2AS\ r AS -CH=CHAS\ c1150 CHEC P--R or As-R CHEC CHECCH2CHZAS\ CH:CHAs\ R2 R2 respectively, to form Rn respectively. AlsoCH=CI-IP GH=CH2 CECH 0 As-CH=CH2 or As-CECH RL-P R" CH=CH2 CECE isreacted with R1 or R /P1I CH=CHA5 r m 10 form R As /R /Rl 1 CHzCHzP\CH=CHP\ 0 R R2 respectively.

Our novel compounds having four or more trivalent its-011mm? orASCII=CHP phosphorus atoms, four or more trivalent arsenic atoms, or acombination of four or more trivalent phosphorus atoms and trivalentarsenic atoms are formed, for example, by reacting reactant compoundshaving three vinyl- CHZCHZP CHZCHP phosphorus or threeethynyl-phosphorus bonds or three vinyl-arsenic bonds or threeethynyl-arsenic bonds with a reactant compound having aphosphorus-hydrogen or an respectively Also, arsenic-hydrogen bond. Forexample,

' CH=CH1 CECII OH=CH2 /CEGH P-CH=CH2 or P-CzCII PCH=CH2 or PCECH CHZCHZCECE CH=CH2 CECH is reacted with 15 reacted Wlth r-n \A5-H respectively.R and R can be the same or difierent. Further, as to our novel processfor making our novel compounds,

respectively. In the foregoing described novel compounds formed R R andR can be the same or different. Also, each substituent R can be the sameor different. AlsO, the two-carbon atom bridge in each of the foregoingrecited reactant comopunds 1 CH2CH2P H H and P CHQCHZP/ H H can bereplaced by the two-carbon atom bridge -CH=CH- The compounds R5 R R R5 PCHzCHzP and ASCHQCHQAs H H H H are formed by cleavage of (R PCH CH P(Rand (R AsCH CH As(R respectively, with sodium metal in liquid ammonia orby the method of Issleib et 211., Ben, 101, 2197 (1968), where R is C HWith respect to n in Formula 2, supra, n is a whole number of at least2, and can be 2, 3, etc. and is preferably 2 or 3. Where n is 3 thephosphorous-hydrogen bond and arsenic-hydrogen bond containing compoundsare respectively, and are formed by cleavage of Ra I (R P-CH2CH -P-CHCHz-P(Rm and respectively, with sodium metal in liquid ammonia, supra.

Also, our novel process is also used in making our novel compoundshaving the general formula Re e BK \RT (3 supra.

For example,

P-OH=OHz or P-OECH is reacted with H\ /H /P CH2CH2P\ H H to form P CH CHCHzCHzP R 1 P CHzCHgP P CHzCHz CHZCHZP R 1 P CH=CH CH=CHP R7 \R7 PCHzCHzP B R P CH=CH CI-I=CHP\ R1 31 respectively. Also,

ASCH=CI{2 or As-OzCII is reacted with II H /P CH2CH2P\ H H to formAsGHzOHz CH CHAs\ R 1 P CHzCHgP R /R ASCHzCHz CHzCHzAS R7 R1 ASCH=CHCH=CHAs 111 R7 P 011201121 R6 a ASCIIzClI CII=OIIAs respectively. Inaddition,

POH=CH or POECII is reacted with H H /ASCHzCHzAS\ H. II

to form P CHgCHz CHzCHz R 111 ASCHgCHzAS R a PCHzCHz CHzCHzP R R R R PCH=CH CH=CHP R 1 AsCHaCHzAs It /no PCH=CH CI-I=CHP\ R B respectively. Inthe foregoing described novel compounds formed R and R can be the sameor different.

In carrying out the foregoing processes a base catalyst is utilized,and, depending upon the particular combination of reactants andcatalyst, our novel processes can be carried out at temperatures rangingfrom about C. through about 350 C., and the preferred temperatures arein the range from about 80 C. through 100 C. Pressures both active andbelow tmospheric pressure as Well at atmospheric pressure are used incarrying out our novel processes, and atmospheric pressure is preferred.In situations wherein one or more of the reactants or the catalyst, orboth, boils below the reaction temperature, pressures above atmosphericpressure are necessary, and sealed pressure vessels are used. Also ininstances where a reactant is gaseous, for example, PH the reaction canbe carried out by generating the reactant and passing it through asolvent such as tetrahydrofuran containing the other reactant and thecatalyst. The weight proportions in which the reactant compounds areused to form the novel compounds of this invention can be varied withinwide limits of their respective molar proportions, that is, 19:1 to1:19, but the use of stoichiometric quantities of the reactant compoundsenable the attainment of readily purifiable high yields of knownpolydentate polytertiary arsine and polytetriary phosphine compounds,for example, from 65 through yields and readily purifiable yields of ournovel compounds in substantially high yields. Also contemplated withinthe scope of our invention are our novel processes using substantiallystoichiometric quantities of reactant compounds to form thesubstantially readily purifiable yields of our novel compounds of thisinvention. In making both the known polydentate compounds and the novelpolydentate compounds of this invention, the use of substantiallystoichiometric amounts of the reactant compounds enables the attainmentof easily and readily purifiable product compounds and highly purifiedproduct compounds, respectively. In those instances where at least oneof the reactants and some of the catalystes oxidize rapidly when exposedto air, our novel process is carried out in an inert atmosphere, andpreferably nitrogen because of its low cost, but other inert gaseousatmospheres such as an argon or a helium atmosphere can be used. Also,our novel process can be carried out in a vacuum. The basic catalystsare used in amounts varying within wide limits and preferably inrelatively small amounts with respect to the total weight of thereactants, for example, 0.0l%-20%, and preferably 1l0%, by weight of thetotal weight of the reactants.

The base catalysts used in carrying out the novel pr0c-= esses of ourinvention are alkyllithium compounds where= in the alkyl group has 1through 70 carbon atoms, and preferably 1 through 12 carbon atoms,aryllithiums wherein the aryl group has 1 through 12 carbon atoms, andpreferably phenyllithium, alkoxides of alkali metals, alkoxides ofalkaline earth metals and alkoxides of lanthanide elements, for example,sodium tert-butoxide and potassium tert-butoxide, and preferablypotassium tert-butoxide, dialkylamido derivatives of alkali metals,dialkylamido derivatives of alkaline earth metals and dialkylamidoderivatives of lanthanide elements, for example, lithium dimethylamidehaving the formula CH LiL arylamido derivatives of alkali metals,arylamido derivatives of alkaline earth metals and arylamido derivativesof lanthanide elements, arylalkylamido derivatives of alkali metals,arylalkylamido derivatives of alkaline earth metals and arylalkylamidoderivatives of lanthanide elements, for example, the sodium derivativeof N-methylaniline having the formula diarylamido derivatives of alkalimetals, diarylamido derivatives of alkaline earth metals and diarylamidoderivatives of lanthanide elements, strongly basic amines, for example,pentamethylguanidine, and mixtures of one or more of the foregoing basecatalysts.

Also, in carrying out our novel processes, an inert diluent, in whichthe reactant compounds and the catalyst are stable and in which thereactants have some solubility, can be used. Among the diluents arehydrocarbons, such as hexane, heptaue, benzene, toluene, xylene,mesitylene, Tetralin, etc., and ethers, alcohols, etc. However, an inertdiluent is not essential.

The following examples illustrate details of procedures which may befollowed. However, the following examples are given only for the purposeof illustration and are not to be construed as limiting our invention inany way.

EXAMPLE 1 A mixture of two (2) grams (.0167 mole) of trivinylphosphineand ten grams (.0538 mole) of diphenylphosphine, 10 grams of a 1 molarsolution of phenyllithium in 70:30 benzene-ether, and 100 grams of drybenzene was boiled under reflux in a nitrogen atmosphere for hours. Thereaction mixture was cooled to room temperature, and the solvent wasremoved in a water aspirator vacuum. The residue was washed withmethanol and then was recrystallized from a mixture of methanol andbenzene, and the yield was 7 grams (.0105 mole) of tris(Z-diphenylphosphinoethyl)phosphine having the formula phenyl CHzCHaPphenyl phenyl P CHzCHrP used as a tetradentate ligand in forming metalcomplexes. The compound has a melting point of 131 C.

14 Analysis.Calculated for C H P (percent): C, 75.3; H, 6.3; P, 18.4(mol. wt. 670). Found (percent): C, 75.1;

H, 6.5; P, 17.9 (mol. wt. 667).

EXAMPLE 2 A mixture of two grams (.0167 mole) of trivinylphosphine, ten(10) grams (.0538 mole) of diphenylphosphine, one (1) gram of potassiumtert-butoxide, and grams of dry benzene was boiled under reflux in anitrogen atmosphere for 12 hours. The product Was isolated in the samemanner as in Example 1 to yield 7 grams (.0105 mole) oftris(2-diphenylphosphinoethyl) phosphine having a melting point of128-129 C. and was shown by its infrared spectrum to be identical to thecompound prepared in Example 1. The yield was approximately 63%.

EXAMPLE 3 A stainless steel pressure vessel was charged with 100 gramsof dry benzene, 10 grams of a 1 molar solution of phenyllithium in 70:30benzene-ether, and 30 grams (.142 mole) of diphenylvinylphosphine. Aftercooling in a liquid nitrogen bath the vessel was charged with about 3grams (.09 mole) of phosphine (PH The vessel was heated in an oven at100 C. for 36 hours. The vessel was then cooled and the solvent wasremoved in a water aspirator vacuum. Vacuum distillation of theresulting brown oil resulted in the recovery of 20 grams (.095 mole) ofthe diphenylvinylphosphine. Ten grams (.047 mole) ofdiphenylvinylphosphine Were used in the reaction (.142-.095=.047 mole).The distillation residue was recrystallized from a mixture of benzeneand methanol to give 2.5 grams (.004 mole) of white crystallinetris(Z-diphenylphosphinoethyl) phosphine having a melting point ofl29-130 C. The infrared spectrum of this product was identical to thecompound prepared in Example I. To obtain a 100% theoretical yield ofproduct using the molar ratio of 3:1 for diphenylvinylphosphine tophosphine, respectively, the molar ratio of the product to thediphenylvinylphosphine would be 1:3 and the molar ratio of the productto the phosphine would be 1:1. An excess of phosphine gas was used, andthe yield, based upon the reaction of .047 mole ofdiphenylvinylphosphine and .016 mole of phosphine gas, was approximately25%.

EXAMPLE 4 A mixture of 4 grams (.0163 mole) of l,2-bis(phenylphosphine)ethane having the formula 7 grams (.033 mole) of diphenylvinylphosphine,0.6 gram of potassium tert-butoxide, and 100 grams of dry benzene wasboiled under reflux in a nitrogen atmosphere for 24 hours. The reactionmixture was cooled to room temperature and the solvent was removed in awater aspirator vacuum. The residue was washed with methanol and thenwas recrystallized twice from mixtures of benzene and methanol to give5.6 grams (.0084 mole) of l,l,4,7,10,10- hexaphenyl 1,4,7,10tetraphosphadecane having the formula having a melting point of 158 C.The yield obtained was approximately 51.5%. This compound can be used asa tetradentate ligand in forming metal compounds.

Analysis.Calculated for C H P4 (percent): C,

75.3; H, 6.3; P, 18.4 (molecular weight 670). Found per)cent): C, 74.3;H, 6.3; P, 17.9 (molecular weight EXAMPLE 5 A mixture of 21 grams (.099mole) of diphenylvinylphosphine, 2 grams (.022 mole) of1,2-diphosphinoethane, 15 grams of 1 molar phenyllithium in 70:30benzeneether, and 150 grams of dry benzene was boiled under reflux in anitrogen atmosphere for 24 hours. The reaction mixture was cooled toroom temperature, and the solvent was then removed in a water aspiratorvacuum. Unreacted diphenylvinylphosphine in the amount of 16 grams (.075mole) was removed from the resulting liquid by distillation at 121C./0.5 mm., as in Example 3, supra, and the residue was recrystallizedfrom a mixture of benzene and methanol. The yield of the productcompound 1,1,4,4 tetrakis(2 diphenylphosphinoethyl) 1,4 diphosphabutanehaving the formula CaH5 C5115 PC 2CH2 CHzCHzP P CHzCHzP CsHs C5115PCHzCHg CHzCHzP 6 Ca s was 1.2 grams (.0013 mole) having a melting pointof 138-140 C. This product compound can be used as a hexadentate ligandin forming metal complexes.

Analysis-Calculated for C H P (percent): C, 73.9; H, 6.4; P, 19.7(molecular weight 952). Found (percent): C, 71.9; H, 6.4; P, 20.9(molecular weight 950).

A yield of about 21.3% of product compound was obtained.

EXAMPLE 6 A mixture of 5 grams (.024 mole) of diphenylvinylphosphine,5.4 grams (0.23 mole) of diphenylarsine, 0.5 gram of potassiumtert-butoxide, and 100 grams of dry benzene was boiled under reflux in anitrogen atmosphere for 24 hours. The reaction mixture was cooled toroom temperature and solvent was then removed in a water aspiratorvacuum. After washing with methanol the residue was recrystallized froma mixture of methanol and benzene, and 8 grams (.019 mole) of whitecrystalline ldiphenylphosphino-Z diphenylarsinoethane having the formulac 5H5 C6 15 P-o mom-As e a C0115 was obtained. This product can be usedas a bidentate ligand in forming metal complexes. The yield was about82.5%.

Analysis.Calculated for C H 'AsP (percent): C, 70.6; H, 5.5; As, 16.9;P, 7.0 (molecular weight 442). Found (percent): C, 69.8; H, 5.5; As,17.5; P, 7.0 (molecular weight 441).

EXAMPLE 7 A mixture of 2 grams (.0095 mole) of diphenylethynylphosphine,2.2 grams (.0095 mole) of diphenylarsine, 0.3 gram of potassiumtert-butoxide, and 100 grams of dry benzene was boiled under reflux in anitrogen atmosphere for 24 hours. After cooling to room temperature thesolvent was removed from the reaction mixture in a water aspiratorvacuum. After washing with methanol, the residue was crystallized from amixture of benzene and methanol to yield 3.5 grams (.0080 mole) oftrans-l-diphenyl-phosphino-2-diphenylarsinoethylene having the formulaCsHs C0115 C=C\ Call- /A H CaHs having a melting point of 95-96 C. Theyield was approximately 84.5%. The proton n.m.r. spectrum of the productcompound exhibited a strong somewhat broad phenyl resonance at 2.7-2.8and two relatively weak doublet vinyl resonances at 1307 (1:145 c.p.s.)and 73.10 (J =16 c.p.s.). The greater similarity of this spectrum to thereported spectrum in Aguiar et al., J. Am. Chem. Soc., 86, 2299 (1964)of trans- (C H5) (C H5) 2 than that of the corresponding cis-isomerindicates this product to be rather than the corresponding cis isomer.This product compound can be used as a bidentate ligand in forming metalcomplexes.

Analysis.Calculated for C H AsP (percent): C, 70.9; H, 5.0; As, 17.1; P,7.0 (molecular weight 440). Found (percent): C, 70.8; H, 5.0; As, 16.9;P, 7.1; (molecular weight 441).

EXAMPLE 8 A mixture of 2 grams (.0123 mole) of phenyldivinylphosphine,5.8 grams (.0252 mole) of diphenylarsine, 0.5 gram of potassiumtert-butoxide, and grams of dry benzene was boiled under reflux in anitrogen atmosphere for 20 hours. After cooling to room temperature thesolvent was removed in a water pump vacuum. The residue was washed withmethanol and then recrystallized from a mixture of benzene and methanolto yield 3.6 grams (.0058 mole) of bis(2-diphenylarsinoethyl)phenylphosphine having the formula CH2CH2AS CHZCI'IZAS C l-I having amelting point of 162 C. The yield was approximately 47.2%. This productcompound can be used as a tridentate ligand in forming metal complexes.

Analysis.-Calculated for C H As P (percent): C,

65.5; H, 5.3; P, 5.0 (molecular weight 622). Found (percent): C, 64.3;H, 5.1; P, 5.2 (molecular weight 623).

EXAMPLE 9 A mixture of 5 grams (.023 mole) of diphenylvinylphosphine,4.3 grams (.023 mole) of diphenylphosphine, 4 grams of a 1 molarsolution of phenyllithium in 70:30 benzene-ether, and 100 grams ofbenzene was boiled under reflux for 20 hours. After cooling to roomtemperature the solvent was removed in a water pump vacuum. The residuewas washed with methanol and then recrystallized from a mixture ofmethanol and benzene to yield 7.5 grams (.019 mole) of1,2-bis(diphenylphosphino)-ethane having the formula CsHsP CaHs Ca s P CH20 Hz? C5115 CtHS having the melting point of 139-140" C. The yield wasapproximately 83%. This product compound can be used as a bidentateligand in forming metal complexes. The infrared spectrum of this productcompound was identical to that of the 1,2-bis(diphenylphosphino)-ethaneprepared from lithium diphenylphosphide and 1,2-dich1orethane [seeHewertson et al., J. Chem. Soc., 1490 (1962)].

EXAMPLE 10 A mixture of 3 grams (.0143 mole) a slight excess was used]of diphenylethynylphosphine, 2.6 grams (.0140 mole) ofdiphenylphosphine, 2 grams of 1 molar solution of phenyllithium in 70:30benzene-ether and 100 grams of benzene was boiled under reflux for 14hours. After cooling to room temperature the solvent was removed fromthe reaction mixture in a water aspirator vacuum.

The residue was then washed with methanol and recrystallized from amixture of methanol and benzene to yield 3.7 grams (.0093 mole) of whitecrystalline trans- (C H (C H5 2 having the melting point 123-l24 C. Theyield of the product compound was approximately 66.3%, the structuralformula of said compound being The infrared and proton n.m.r. spectra ofthe product compound and the infrared and proton n.m.r. spectra of thetrans-(C H PCH=CHP(C H prepared from trans-1,2-dichloroethylene lithiumdiphenylphosphide [see Aguiar et al., J. Am. Chem. Soc., 86, 2299(1964)] and were identical. This product compound can be used as abidentate ligand in forming metal complexes.

EXAMPLE 11 PCHzCHz CeHs having a melting point of 129-130 C. The yieldwas approximately 76%. This product compound can be used as a tridentateligand in forming metal complexes.

Analysis.Calculated for C H P (percent): C, 76.5; H, 6.2; P, 17.3(molecular weight 534). Found (percent): C, 76.2; H, 6.2; P, 17.2(molecular weight 534 (mass spec.)

EXAMPLE 12 A mixture of grams (.094 mole) of diphenylvinylphosphine, 5.2grams (.047 mole) of phenylphosphine, 5 grams of a 1 molar solution ofphenyllithium in 70:30 benzene-ether and 150 grams of dry benzene wasboiled under reflux in a nitrogen atmosphere for 24 hours. After coolingto room temperature the solvent was removed in a water pump vacuum. Theresidue Was washed with methanol and then recrystallized from a mixtureof methanol and benzene to yield 18 grams (.034 mole) ofbis(2-diphenylphosphinoethyl) phenylphosphine having the formula CansP-CHzCITz having the melting point of l28-l29 C. The yield wasapproximately 71.3%. The infrared spectrum of this product compound wasidentical to the product compound of Example 11, supra. This productcompound can be used as a tridentate ligand in forming metal complexes.

1 8 EXAMPLE 13 A mixture of 10 grams (.047 mole) ofdiphenylvinylphosphine, 2.6 grams (.0235 mole) of phenylphosphine, 0.5grams of potassium tert-butoxide, and grams of dry benzene was boiledunder reflux in a nitrogen atmosphere for 24 hours. After cooling toroom temperature the solvent was removed in a water aspirator vacuum.The residue was washed with methanol and recrystallized from a mixtureof methanol and benzene to yield 11 grams (.0206 mole) of whitecrystalline bis(2-diphenylphos phinoethyl) phenylphosphine having theformula P-CtHs having the melting point of 127 C. The yield wasapproximately 87.5%. The infrared spectrum of this product compound wasidentical to the product compound of Example 11, supra. Also, theproduct compound herein can be used as a tridentate ligand in formingmetal complexes.

EXAMPLE 14 A mixture of 10 grams (.047 mole) of diphenylvinylphosphineand 0.6 gram of potassium tert-butoxide was added to grams oftetrahydrofuran and the mixture was boiled under reflux. Then 3 grams(.09 mole) of phosphine gas, generated from aluminum phosphide indioxane and water was bubbled through the boiling under reflux mixturein tetrahydrofuran for 3 hours. The mixture was then cooled and thetetrahydrofuran was recovered by pumping it off under vacuum. Theresidue was washed with methanol and recrystallized from a mixture ofmethanol and benzene to yield 9.5 grams (.0142 mole) of whitecrystalline tris(Z-diphenylphosphinoethyl) phosphine having the formulaCoHtS CHgCHnP CaHs P-CHzCHzP CHQCHzP having the melting point of 131 C.The infrared spectrum of this product compound was identical to thecompound prepared in Example 1, supra. The yield was approximately 89%.An excess of phosphine was used.

Additional product compounds using reaction conditions and reactantamounts and catalysts similar to the foregoing examples are prepared,and to save repetitive details, are presented in Table I, setting forththe reactant compounds and the product compounds, as follows:

TABLE I Example 15 Reactant compound 1 )--(C H PH Reactant compound (2)(CH N] PCH=CH Mole ratio of (l) to (2)-1 :1

Pr0duct-( C6H5 2] 2 Yield-approximately 84% CatalystphenyllithiumExample 16 Reactant compound (1)-CH PH Reactant compound (2)-(C H PCH=CHMole ratio of (1) to (2)-1:2

1 9 TABLE IExample 16--Contd. ProductCH P[CH CH2 6 )2]2Yieldapproximately 87% Catalyst-potassium tert-butoxide Example 17Reactant compound (1)(C H PH Reactant compound (2)(C H O) PCH=CHCH Moleratio of (1) to (2)-1:1 Product(C H O) PCH CH (CH P (C H 2Yield-approximately 79% Catalyst-phenyllithium Example 18 Reactantcompound (1)(C H PH Reactant compound (2)(C H 2PCEC (OC H Mole ratio of(1) to (2)-1:1 'Product (C H PC(OC H )=CHP (C H 2 Yield-approximately 81Catalyst-potassium tert-butoxide Example 19 Reactant compound (1) C HP(H)CH CH P (C H )CH CH P(I-l)C H iReactant compound (2) (CH PCH=CH Moleratio of (1) to (2)--1:2 PIOdUCt (CH 2P (C5H5) CH CH P(CH 2Yield-approximately 64% Catalystphenyllithium Example 20 Reactantcompound (1)--H PCH CH(CH PH Reactant compound (2 )(CH PCH=CH Mole ratioof (1) to (2)-1:4 Product- [(CH PCH CH PCH CH(CH P 2 z 3) 2] 2Y1eldapproximately 68% Catalystphenyllithium Example 21 Reactantcompound (1)(C H (CH )PH Reactant compound (2)(C H (CH )PCH=CH Moleratio of (l) to (2)1:l

PI'OdllCt(C H5) (C H Yield-approximately 85% Catalyst-potassiumtert-butoxide Example 22 Reactant compound 1 )(C H PH Reactant compound(2)-(p-CH C H PCH=CH Mole ratio of (l) to (2)-1 :1 PI'OdUCt-(p-CH C5H4(C5H5 2 Yieldapproximately 89% Catalyst-phenyllithium In carrying outthe novel processes, including those in Examples 1-22, inclusive, of ourinvention, aryllithium catalysts, for example, phenyllithium, andalkyllithium catalysts are not used in reactions wherein diphenylarsineis one of the reactants. In determining the molecular weights of each ofthe compounds hereinbefore described in detail, a Mechrolab vaporpressure osmometer using benzene as the solvent for the compound whosemolecular weight was under determination was used. In the novelprocesses herein described in detail there was carried out the basecatalyzed addition of a phosphorus-hydrogen bond or an arsenic-hydrogenbond across a carbon-carbon double bond or a carbon-carbon triple bond,and the product compounds did not contain any phosphorushydrogen bond orarsenic-hydrogen bond. As is readily apparent from the foregoingdetailed description, where one react-ant has only onephosphorus-hydrogen bond or one arsenic-hydrogen bond and the otherreactant has only one carbon-carbon double or triple bond, the ratio ofthe number of moles of the carbon-carbon double or triple bondcontaining reactant to the number of moles of phosphorus-hydrogen orarsenic-hydrogen bond containing react-ant is 1:1. Where one reactantcompound has two phosphorus-hydrogen or two arsenic-hydrogen bonds andthe other reactant has only one carbon-carbon double or triple bond, theratio of the number of moles of the carbon-carbon double or triple bondcontaining reactant to the number of moles of the phosphorus-orarsenichydrogen bond containing reactant is in the ratio of 2:1. Whereone reactant compound has three phosphorusor arsenic-hydrogen bonds, andthe other reactant has only one carbon-carbon double or triple bond, theratio of the number of moles of the carbon-carbon double or triple bondcontaining reactant to the number of moles of the phosphorusorarsenic-hydrogen bond containing reactant is 3:1. Where one reactantcompound has four phosphorusor arsenic-hydrogen bonds and the otherreactant has only one carbon-carbon double or triple bond, the ratio ofthe number of moles of the carboncarbon double or triple bond containingreactant to the number of moles of the phosphorusor arsenic-hydrogenbond containing reactant is 4:1. Likewise, where one reactant compoundhas only one carbon-carbon double or triple bond, the ratio of thenumber of moles of it to the number of moles of the reactant having onlyone phosphorusor arsenic-hydrogen bond is 1:1. Where one reactantcompound has two carbon-carbon double or triple bonds, the ratio of thenumber of moles of it to the number of moles of the reactant having onlyone phosphorusor arsenichydrogen bond is 2:1. Where one reactantcompound has three carbon-carbon double or triple bonds, the ratio ofthe number of moles of it to the number of moles of the reactant havingonly one phosphorusor arsenic-hydrogen bond containing reactant is 3:1.

The novel polydentate polytertiary phosphines and arsines andarsino-phosphines of our invention are useful as ligands for makingcomplexes with metal carbonyls and metal halides useful as catalysts forpolymerization and oligomerization of olefins and acetylenes. Themultidentate character of our novel compounds contribute to theeffectiveness of the resulting so-formed catalysts with said carbonylsand halides. Complexes of our novel compounds with nickel carbonyloligomerize or polymerize, for example, butadiene. Also, mixtures of ournovel compounds with halides of titanium, zirconium, vanadium, niobium,and related metals, in the presence of aluminum alkyls are useful forproducing polyethylene. Further, nickel complexes of our novel compoundsin the presence of sodium borohydride are useful for the polymerizationof acetylenes.

Many alterations and changes may be made without departing from thespirit and scope of this invention which is set forth in the appendedclaims which are to be construed as broadly as possible in view of theprior art.

We claim:

1. A polydentate selected from the group consisting of (1) X(AYR Rwherein X is a member in its trivalent state selected from the groupconsisting of phosphorus and arsenic, Y is a member in its trivalentstate selected from the group consisting of phosphorus and arsenic, A isa member selected from the group consisting of wherein tR is a memberselected from the group consisting of hydrogen, alkyl, aromatichydrocarbon, alkoxy substitution products of said alkyl and aromatichydrocarbon, and dialkylamino substitution products of said alkyl andaromatic hydrocarbon, with the proviso that at least one R" is hydrogen,and each of R and R is a member selected from the group consisting ofalkyl, aromatic hydrocarbon, alkoxy substitution products of said alkyland aromatic hydrocarbon, and dialkylamino substitution products of saidalkyl and aromatic hydrocarbon;

n is a whole number of at least 2,

X is a member in its trivalent state selected from the group consistingof phosphorus and arsenic,

Y is a member in its trivalent state selected from the group consistingof phosphorus and arsenic, with the proviso that X is always the same,

A is a member selected from the group consisting of wherein X is amember in its trivalent state selected from the group consisting ofphosphorus and arsenic,

Y is a member in its trivalent state selected from the group consistingof phosphorus and arsenic, with the proviso that all of the X and Ymembers are never all arsenic and X is always the same,

A is a member selected from the group consisting of wherein R is amember selected from the group consisting of hydrogen, alkyl, aromatichydrocarbon, alkoxy substitution products of said alkyl and aromatichydrocarbon, and dialkylamino substitution products of said alkyl andaromatic hydrocarbon, with the proviso that at least one R is hydrogen,and each of R and R is a member selected from the group consisting ofalkyl, aromatic hydrocarbon, alkoxy substitution products of said alkyland aromatic hydrocarbon, and dialkylamino substitution prodnets of saidalkyl and aromatic hydrocarbon; and

wherein m is a whole number from 1-2, inclusive,

X is a member in its trivalent state selected from the group consistingof phosphorus and arsenic,

Y is a member in its trivalent state selected from the group consistingof phosphorus and arsenic, with the proviso that X and Y are different,

A is a member selected from the group consisting of -CR=CR- and -CR CRwherein R is a member selected from the group 22 consisting of hydrogen,alkyl, aromatic hydrocarbon, alkoxy substitution products of said alkyland aromatic hydrocarbon, and dialkylamino substitution products of saidalkyl and aromatic hydrocarbon, with the proviso that at least one R" ishydrogen, and each of R, R and R is a member selected from the groupconsisting of alkyl, aromatic hydrocarbon, alkoxy substitution productsof said alkyl and aromatic hydrocarbon, and dialkylamino substitutionproducts of said alkyl and aromatic hydrocarbon,

the number of carbon atoms in the aforestated alkyl groups being from 1through 70, the number of carbon atoms in the aforestated aromatichydrocarbon groups being from 6 through 24, the number of carbon atomsin the aforestated alkoxy substituent groups of the aforestated alkoxysubstituted alkyl groups and aromatic hydrocarbon groups being from 1through 70, and the number of carbon atoms in the alkyl group ofaforestated dialkylamino substituent groups of the aforestateddialkylamino substituted alkyl groups and aromatic hydrocarbon groupsbeing from 1 through 70. 2. The polydentate compound of claim 1 havingthe formula X(AYR R wherein X is a member in its trivalent stateselected from the group consisting of phosphorus and arsenic,

Y is a member in its trivalent state selected from the group: consistingof phosphorus and arsenic,

A is a member selected from the group consisting of --CR=CR-- and --CRCR wherein R is a member selected from the group consisting of hydrogen,alkyl, aromatic hydrocarbon, alkoxy substitution products of said alkyland aromatic hydrocarbon, and dialkylamino substitution products of saidalkyl and aromatic hydrocarbon, with the proviso that at least one R ishydrogen, and

each of R and R is a member selected from the group consisting of alkyl,aromatic hydrocarbon, alkoxy substitution products of said alkyl andaromatic hydrocarbon, and dialkylamino substitution products of saidalkyl and aromatic hydrocarbon.

3. The polydentate compound of claim 1 having the formula wherein n is awhole number of at least 2,

X is a member in its trivalent state selected from the group consistingof phosphorus and arsenic,

Y is a member in its trivalent state selected from the group consistingof phosphorus and arsenic, with the proviso that X is always the same,

A is a member selected from the group consisting of --C-R=CR- and -CR CRwherein R is a member selected from the group consisting of hydrogen,alkyl, aromatic hydrocarbon, alkoxy substitution products of said alkyland aromatic hydrocarbon, and dialkylamino substitution products of saidalkyl and aromatic hydrocarbon, with the proviso that at least one R ishydrogen, and

each of R R and R is a member selected from the group consisting ofalkyl, aromatic hydrocarbon, alkoxy substitution products of said alkyland aromatic hydrocarbon, and dialkylamino substitution products of saidalkyl and aromatic hydrocarbon.

23 4. The polydentate compound of claim 1 having the formula wherein Xis a member in its trivalent state selected from the group consisting ofphosphorus and arsenic,

Y is a member in its trivalent state selected from the group consistingof phosphorus and arsenic, with the proviso that all of the X and Ymembers are never all arsenic and X is always the same,

A is a member selected from the group consisting of C R=CR-- and CR CRwherein R is a member selected from the group consisting of hydrogen,alkyl, aromatic hydrocarbon, alkoxy substitution products of said alkyland aromatic hydrocarbon, and dialkylamino substitution products of saidalkyl and aromatic hydrocarbon, with the proviso that at least one R ishydrogen, and

each of R and R is a member selected from the group consisting of alkyl,aromatic hydrocarbon, alkoxy substitution products of said alkyl andaromatic hydrocarbon, and dialkylamino substitution products of saidalkyl and aromatic hydrocarbon.

5. The polydentate compound of claim 1 having the formula R X(AYR Rwherein m is a whole number from l-2, inclusive,

X is a member in its trivalent state selected from the group consistingof phosphorus and arsenic,

Y is a member in its trivalent state selected from the group consistingof phosphorus and arsenic, with the proviso that X and Y are different,

A is a member selected from the group consisting of CR=CR and CR -CRwherein R is a member selected from the group consisting of hydrogen,alkyl, aromatic hydrocarbon, alkoxy substitution products of said alkyland aromatic hydrocarbon, and dialkylamino substitution products of saidalkyl and aromatic hydrocarbon, with the proviso that at least one R" ishydrogen, and

each of R R and R is a member selected from the group consisting ofalkyl, aromatic hydrocarbon, alkoxy substitution products of said alkyland aromatic hydrocarbon, and dialkylamino substitution products of saidalkyl and aromatic hydrocarbon.

6. The polydentate compound of claim 2 wherein X is phosphorus, Y isphosphorus, A is CH CH -R is phenyl, and R is phenyl, said compoundbeing tris (2- diphenylphosphinoethyl) phosphine having the formulaphenyl CHzCHzP phenyl phcnyl PCII:CH2P

phenyl phenyl (lllzClIzl phenyl 7. The polydentate compound of claim 3wherein n is 2, is phosphorus, Y is phosphorus, A is -CH CH R phenyl, Ris phenyl, and R is phenyl, said compound being1,l,4,7,l0,10-hexaphenyl-l,4,7,10-tetraphosphadecane having the formulaphenyl phenyl 8. The polydentate compound of claim 3 wherein n is, 3, Xis phosphorus, Y is phosphorus, A is -CH CH R is methyl, R is methyl,and R is phenyl, said compound being 1,1,13,13 tetramethyl 4,7,10triphenyl- 1,4,7,l0,l3-pentaphosphatridecane having the formula phenylhenyl 9. The polydentate compound of claim 4 wherein X is phosphorus, Yis phosphorus, A is CH CH R is phenyl, and R is phenyl, said compoundbeing l,1,4,4- tetrakis (Z-diphenylphosphinoethyl)-1,4-diphosphabutanehaving the formula phenyl P CH2CH2 P phenyl phenyl phenyl phenyl phenylphenyl 12. The polydentate compound of claim 5 wherein m is 1, X isphosphorus, Y is arsenic, A is CH CH R is phenyl, and R is phenyl, saidcompound being his (2- diphenylarsinoethyl) phenylphosphine having theformula phenyl CHzCHzAS phenyl phenyl CHzCHgAS phenyl 13. The processfor preparing a polydentate compound comprising reacting, in contactwith a base catalyst,

(1) a reactant compound selected from the group consisting of (a) aphosphine having at least one phosphorushydrogen bond and (b) an arsinehaving at least one arsenic-hydrogen bond with (2) a reactant compoundselected from the group consisting of (a) a phosphine having at leastone vinyl-phosphorus bond,

phenyl phonyl-P (b) an arsine having at least one vinyl-arsenic bond,

() a phosphine having at least one ethynyl-phosphorus bond, and

(d) an arsine having at least one ethynyl-arsenic bond,

with the proviso that each of the phosphorus and the arsenic is in itstrivalent state, and with the further provisos (1) that reactantcompound (1) is free of a vinylphosphorus bond, a vinyl-arsenic bond, anethynyl-phosphorus bond and an ethynyl-arsenic bond and reactantcompound (2) is free of a phosphorus-hydrogen bond and anarsenic-hydrogen bond,

(2) that reactant compound (1) has only one phosphorus-hydrogen bond orarsenic-hydrogen bond if reactant compound (2) has a plurality ofvinyl-phosphorus bonds, vinyl-arsenic bonds, ethynyl-phosphorus bonds orethynyl-arsenic bonds,

(3) that reactant compound (1) has only one vinyl-phosphorus bond,vinyl-arsenic bond, ethynyl-phosphorus bond or ethynyl-arsenic bond ifreactant compound (2) has a plurality of phosphorus-hydrogen bonds orarsenic-hydrogen bonds, and

(4) that an alkyllithium and an aryllithium are not used as basecatalysts if reactant compound (1) is diphenylarsine.

14. The process of claim 13 wherein the base catalyst is a memberselected from the group consisting of (1) an alkyllithium,

(2) an aryllithium,

(3) an alkoxide of a member selected from the group consisting of alkalimetals, alkaline earth metals and lanthanide elements,

(4) a dialkylamido derivative of a member selected from the groupconsisting of alkali metals, alkaline earth metals and lanthanideelements,

(5) an arylalkylamido derivative of a member selected from the groupconsisting of alkali metals, alkaline earth metals and lanthanideelements,

(6) a diarylamido derivative of a member selected from the groupconsisting of alkali metals, alkaline earth metals and lanthanideelements,

(7) strongly basic amines, and

(8) mixtures thereof.

15. The process of claim 14 wherein the base catalyst is phenyllithium.

16. The process of claim 14 wherein the base catalyst is potassiumtert.-butoxide.

References Cited UNITED STATES PATENTS 3,086,053 4/1963 Wagner 260-6065P 3,086,054 4/1963 Chatt et a1 260-6065 P 3,253,033 5/1966 Maier260-6065 P 3,518,312 6/1970 Maier 260-6065 P JAMES E. POER, PrimaryExaminer W. F. W. BELLAMY, Assistant Examiner US. Cl. X.R. 260-6065 P

